Heteroaromatic compounds for organic electronics

ABSTRACT

The present invention provides compounds of formula (I) wherein X is O, S or NR 10 , wherein R 10  is H, C 1-30 -alkyl, substituted C 1-30 -alkyl, C 2-30 -alkenyl, substituted C 2-30 -alkenyl, C 2-30 -alkynyl, substituted C 2-30 -alkynyl or C(0)-OR, R 1  and R 11  are independently from each other selected from the group consisting of C 1-30 -alkyl, substituted C 1-30 -alkyl, C 2-30 -alkenyl, substituted C 2-30 -alkenyl, C 2-30 -alkynyl, substituted C 2-30 -alkynyl, C 5-8 -cycloalkyl, substituted C 5-8 -cycloalkyl, C 5-8 -cycloalkenyl, and substituted C 5-8 -cycloalkenyl, and an electronic device comprising the compounds as semiconducting material.

Organic semiconducting materials can be used in electronic devices suchas organic photovoltaic devices (OPVs), organic field-effect transistors(OFETs), organic light emitting diodes (OLEDs), and organicelectrochromic devices (ECDs).

For efficient and long lasting performance, it is desirable that theorganic semiconducting material-based devices show high charge carriermobility as well as high stability, in particular towards oxidation byair.

Furthermore, it is desirable that the organic semiconducting materialsare compatible with liquid processing techniques such as spin coating asliquid processing techniques are convenient from the point ofprocessability, and thus allow the production of low cost organicsemiconducting material-based electronic devices. In addition, liquidprocessing techniques are also compatible with plastic substrates, andthus allow the production of light weight and mechanically flexibleorganic semiconducting material-based electronic devices.

The use of pyrrolobis(benzothiazines) as semiconducting material isknown in the art.

Hong, W.; Wei, Z.; Xu, W.; Wang, Q.; Zho, D. Chinese Journal ofChemistry (2009), 27(4), 846-849 describes

which are air-stable and promising n-type semiconducting materials foruse in organic electronics.

Hong, W.; Wei, Z.; Xi, H.; Xu, W.; Hu, W.; Wang, Q. Zhu, D. J. Mater.Chem. 2008, 18, 4814-4820 describes

and field effect transistors comprising these compounds as p-typesemiconducting compounds.

An organic field effect transistor comprising compound of formula 1 assemiconducting material shows a mobility of 0.34 cm² V⁻¹s⁻¹ (whendeposited by vacuum deposition at 60° C. substrate temperature), butcompound 1 was found to be only slightly soluble in THF, hot DMF andDMSO. An organic field effect transistor comprising compound of formula2 as semiconducting material shows a mobility of only 1.77×10⁻⁴ cm²V⁻¹s⁻¹ (when deposited by vacuum deposition at 60° C. substratetemperature), however compound 2 was found to very soluble in CH₂Cl₂. Anorganic field effect transistor comprising compound of formula 3 assemiconducting material shows a mobility of only 3.01×10-3 cm² V⁻¹s⁻¹(when deposited by vacuum deposition at 60° C. substrate temperature),however compound 3 was found to very soluble in CH₂Cl₂.

Wei, Z.; Hong, W.; Geng, H.; Wang, C.; Liu, Y.; Li, R.; Xu, W.; Shuai,Z.; Hu, W.; Wang, Q., Zhu, D. Advanced Materials 22 (22), 2010, 2458 to2468 also describes

and field effect transistors comprising these compounds as p-typesemiconducting compounds.

The disadvantage of the compound 1 is the low solubility in organicsolvents. The disadvantages of compounds 2 and 3 is that organic fieldeffect transistors comprising compounds 2 and 3 as semiconductingmaterials show low mobilities.

It was the object of the present invention to provide organicsemiconducting materials, which show high solubility in organic solventsand high stability towards oxidation by air, and which at the same time,when applied as a layer in an organic electronic device, yield organicelectronic devices showing good performance such as high charge carriermobilities.

This object is solved by the compounds of claim 1, the process of claim8, the electronic device of claim 9 and the use of claim 11.

The organic semiconducting materials of the present invention arecompounds of formula

wherein

X is O, S or NR¹⁰

-   -   wherein R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,        substituted C₂₋₃₀-alkynyl or C(O)—OR¹¹,        R¹ and R¹¹ are independently from each other selected from the        group consisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,        substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substituted        C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl, and substituted        C₅₋₈-cycloalkenyl,        R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each        other selected from the group consisting of H, C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,        C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,        substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted        O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl, substituted S—C₁₋₃₀-alkyl,        C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15 membered heteroaryl,        substituted 5 to 15 membered heteroaryl and halogen; or R² and        R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹        together with the C-atoms, to which they are connected, form a 6        to 10 membered aromatic ring system, substituted 6 to 10        membered aromatic ring system, 5 to 12 membered heteroaromatic        ring system or a substituted 5 to 12 membered heteroaromatic        ring system,    -   wherein    -   substituted C₁₋₃₀-alkyl, substituted C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkynyl, substituted O—C₁₋₃₀-alkyl and substituted        S—C₁₋₃₀-alkyl, at each occurrence, are C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, O—C₁₋₃₀-alkyl, respectively,        S—C₁₋₃₀-alkyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,        OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),        C(O)—R^(a), C(O)OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;        substituted C₅₋₈-cycloalkyl, and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl,        C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a), OC(O)—R^(a),        OC(O)OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),        C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;        substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,        substituted 6 to 10 membered aromatic ring system, and        substituted 5 to 12 membered heteroaromatic ring system, at each        occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10        membered aromatic ring system, respectively, 5 to 12 membered        heteroaromatic ring system, which are substituted with at least        one substituent independently selected from the group consisting        of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl,        C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,        OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),        C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂, wherein at least one        CH₂-group, but not adjacent CH₂-groups, of C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,        C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,        substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted        O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, can        be replaced by a linking group selected from the group        consisting of O, S, NR¹², CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O),        C(O)—S, NR¹²—C(O), C(O)—NR¹², OC(O)—NR¹² and NR¹²—C(O)O,    -   wherein    -   R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,        substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted        C₂₋₃₀-alkynyl or C(O)—OR^(d), R^(a), R^(b), R^(c) and R^(d) are        independently from each other and at each occurrence selected        from the group consisting of H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl,        C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl,        and 5 to 12 membered heteroaryl.        C₁₋₂₀-alkyl and C₁₋₃₀-alkyl can be branched or unbranched.        Examples of C₁₋₂₀-alkyl are methyl, ethyl, n-propyl, isopropyl,        n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl,        isopentyl, n-(1-ethyl)propyl, n-hexyl. n-heptyl, n-octyl,        n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,        n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,        n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl        (C₂₀). Examples of C₁₋₃₀-alkyl are C₁₋₂₀-alkyl and n-docosyl        (C₂₂), n-tetracosyl (C₂₄), n-hexacosyl (C₂₆), n-octacosyl (C₂₈)        and n-triacontyl (C₃₀).        C₂₋₂₀-alkenyl and C₂₋₃₀-alkenyl can be branched or unbranched.        Examples of C₂₋₂₀-alkenyl are vinyl, propenyl, cis-2-butenyl,        trans-2-butenyl, 3-butenyl, cis-2-pentenyl, trans-2-pentenyl,        cis-3-pentenyl, trans-3-pentenyl, 4-pentenyl,        2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl,        docenyl, linoleyl (C₁₈), linolenyl (C₁₈), oleyl (C₁₈), and        arachidonyl (C₂₀). Examples of C₂₋₃₀-alkenyl are C₂₋₂₀-alkenyl        and erucyl (C₂₂).        C₂₋₂₀-alkynyl and C₂₋₃₀-alkynyl can be branched or unbranched.        Examples of C₂₋₂₀-alkynyl and C₂₋₃₀-alkynyl are ethynyl,        2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl,        octynyl, nonynyl, decynyl, undecynyl, dodecynyl, undecynyl,        dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,        heptadecynyl, octadecynyl, nonadecynyl and icosynyl (C₂₀).

Examples of C₅₋₆-cycloalkyl are cyclopentyl and cyclohexyl. Examples ofC₅₋₈-cycloalkyl are C₅₋₆-cycloalkyl and cycloheptyl and cyclooctyl.

Examples of C₅₋₆-cycloalkenyl are cyclopentenyl and cyclohenexyl.Examples of C₅₋₈-cycloalkenyl are C₅₋₆-cycloalkenyl and cycloheptenyland cyclooctenyl.

Examples of C₆₋₁₀-aryl are

Examples of C₆₋₁₄-aryl are C₆₋₁₀-aryl and

Examples of 5 to 9 membered heteroaryl are

wherein R¹⁰⁰ is H or C₁₋₂₀-alkyl.

Examples of 5 to 12 membered heteroaryl are 5 to 9 membered heteroaryland

wherein R¹⁰⁰ is H or C₁₋₂₀-alkyl.

Examples of 5 to 15 membered heteroaryl are 5 to 12 membered heteroaryland

wherein R¹⁰⁰ is H or C₁₋₂₀-alkyl.

Examples of halogen are F, Cl, Br and I.

A 6 membered aromatic ring system is

wherein the C-atoms marked with * are the C-atoms, to which R² and R³,R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, respectively, R⁸ and R areconnected.

Examples 6 to 10 membered aromatic ring system are

wherein the C-atoms marked with * are the C-atoms, to which R² and R³,R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, respectively, R⁸ and R areconnected.

Examples of 5 to 9 membered heteroaromatic ring system are

wherein R¹⁰⁰ is H or C₁₋₂₀-alkyl,wherein the C-atoms marked with * are the C-atoms, to which R² and R³,R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, respectively, R⁸ and R areconnected.

Examples of 5 to 12 membered heteroaromatic ring system are 5 to 9membered heteroaromatic ring systems and

wherein R¹⁰⁰ is H or C₁₋₂₀-alkyl, andwherein the C-atoms marked with * are the C-atoms, to which R² and R³,R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, respectively, R⁸ and R areconnected.

In preferred compounds of formula (1)

X is O, S or NR¹⁰,

-   -   wherein R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl or C(O)—OR¹¹,        R¹ and R¹¹ are independently from each other selected from the        group consisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,        substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substituted        C₅₋₈-cycloalkenyl,        R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each        other selected from the group consisting of H, C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,        C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl,        O—C₁₋₃₀-alkyl, substituted O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl,        substituted S—C₁₋₃₀-alkyl, C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5        to 15 membered heteroaryl, substituted 5 to 15 membered        heteroaryl and halogen; or R² and R³, R³ and R⁴, R⁴ and R⁵, R⁶        and R⁷, R⁷ and R⁸, or, R⁸ and R⁹ together with the C-atoms, to        which they are connected, form a 6 to 10 membered aromatic ring        system, substituted 6 to 10 membered aromatic ring system, 5 to        12 membered heteroaromatic ring system or a substituted 5 to 12        membered heteroaromatic ring system,    -   wherein    -   substituted C₁₋₃₀-alkyl, substituted C₂₋₃₀-alkenyl, substituted        O—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, at each occurrence,        are C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, O—C₁₋₃₀-alkyl, respectively,        S—C₁₋₃₀-alkyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,        OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),        C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;        substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered        heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),        OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;        substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,        substituted 6 to 10 membered aromatic ring system and        substituted 5 to 12 membered heteroaromatic ring system, at each        occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10        membered aromatic ring system, respectively, 5 to 12 membered        heteroaromatic ring system, which are substituted with at least        one substituent independently selected from the group consisting        of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered        heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),        OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)C(O)—R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂,        wherein at least one CH₂-group, but not adjacent CH₂-groups, of        C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,        C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl,        O—C₁₋₃₀-alkyl, substituted O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl and        substituted S—C₁₋₃₀-alkyl, can be replaced by a linking group        selected from the group consisting of O, S, NR¹², CO, O—C(O),        C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR¹²—C(O), C(O)—NR¹²,        OC(O)—NR¹² and NR¹²—C(O)—O,    -   wherein    -   R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, or C(O)—OR^(d),    -   R^(a), R^(b), R^(c) and R^(d) are independently from each other        and at each occurrence selected from the group consisting of H,        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5 to 12 membered        heteroaryl.

In more preferred compounds of formula (1)

X is O, S or NR¹⁰,

-   -   wherein R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or        C(O)—OR¹¹,        R¹ and R¹¹ are independently from each other selected from the        group consisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,        substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substituted        C₅₋₈-cycloalkenyl,        R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each        other selected from the group consisting of H, C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl, substituted        C₅₋₈-cycloalkyl, C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15        membered heteroaryl and substituted 5 to 15 membered heteroaryl;        or R² and R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸        and R⁹ together with the C-atoms, to which they are connected,        form a 6 to 10 membered aromatic ring system, substituted 6 to        10 membered aromatic ring system, 5 to 12 membered        heteroaromatic ring system or a substituted 5 to 12 membered        heteroaromatic ring system,    -   wherein    -   substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each        occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which        are substituted with at least one substituent independently        selected from the group consisting of C₅₋₆-cycloalkyl,        C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a), OC(O)—R^(a),        OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),        C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;    -   substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered        heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),        OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;    -   substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,        substituted 6 to 10 membered aromatic ring system, and        substituted 5 to 12 membered heteroaromatic ring system, at each        occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10        membered aromatic ring system, respectively, 5 to 12 membered        heteroaromatic ring system, which are substituted with at least        one substituent independently selected from the group consisting        of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered        heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),        OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)C(O)—R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂,    -   wherein at least one CH₂-group, but not adjacent CH₂-groups, of        C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl        C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl can be        replaced by a linking group selected from the group consisting        of O, S, NR¹², CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S,        NR¹²—C(O), C(O)—NR¹², OC(O)—NR¹² and NR¹²—C(O)—O,    -   wherein    -   R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or C(O)—OR^(d),    -   R^(a), R^(b), R^(c) and R^(d) are independently from each other        and at each occurrence selected from the group consisting of H,        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5 to 12 membered        heteroaryl.

In even more preferred compounds of formula (1)

X is O, S or NR¹⁰,

-   -   wherein R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or        C(O)—OR¹¹,        R¹ and R¹¹ are independently from each other selected from the        group consisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,        substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substituted        C₅₋₈-cycloalkenyl,        R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each        other selected from the group consisting of H, C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl, substituted        C₅₋₈-cycloalkyl, C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15        membered heteroaryl and substituted 5 to 15 membered heteroaryl;        or R² and R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸        and R⁹ together with the C-atoms, to which they are connected,        form a 6 to 10 membered aromatic ring system, substituted 6 to        10 membered aromatic ring system, 5 to 12 membered        heteroaromatic ring system or a substituted 5 to 12 membered        heteroaromatic ring system,    -   wherein    -   substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each        occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which        are substituted with at least one substituent independently        selected from the group consisting of C₅₋₆-cycloalkyl,        C₆₋₁₀-aryl, and 5 to 12 membered heteroaryl,    -   substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5 to 12 membered        heteroaryl;    -   substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,        substituted 6 to 10 membered aromatic ring system, and        substituted 5 to 12 membered heteroaromatic ring system, at each        occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10        membered aromatic ring system, respectively, 5 to 12 membered        heteroaromatic ring system, which are substituted with at least        one substituent independently selected from the group consisting        of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered        heteroaryl;        wherein at least one CH₂-group, but not adjacent CH₂-groups, of        C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,        C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl can be        replaced by a linking group selected from the group consisting        of O, S, and NR¹²,    -   wherein    -   R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or C(O)—OR^(d),        R^(d) is at each occurrence selected from the group consisting        of H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,        C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, and 5 to 12        membered heteroaryl.

In most preferred compounds of formula (1)

X is S,

R¹ is selected from the group consisting of C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substitutedC₅₋₈-cycloalkenyl,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each otherselected from the group consisting of H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₆-10-aryl,substituted C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, and substituted 5to 12 membered heteroaryl; or R² and R³, R³ and R⁴, R⁴ and R⁵, R⁶ andR⁷, R⁷ and R⁸, or, R⁸ and R⁹ together with the C-atoms, to which theyare connected, form a 6 membered aromatic ring system, substituted 6membered aromatic ring system, 5 to 9 membered heteroaromatic ringsystem or a substituted 5 to 9 membered heteroaromatic ring system,

-   -   wherein    -   substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each        occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which        are substituted with at least one substituent independently        selected from the group consisting of C₅₋₆-cycloalkyl, phenyl        and 5 to 9 membered heteroaryl,    -   substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, phenyl and 5 to 9 membered        heteroaryl,    -   substituted C₆₋₁₀-aryl, substituted 5 to 12 membered heteroaryl,        substituted 6 membered aromatic ring system, and substituted 5        to 9 membered heteroaromatic ring system, at each occurrence,        are C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, 6 membered aromatic        ring system, respectively, 5 to 9 membered heteroaromatic ring        system, which are substituted with at least one substituent        independently selected from the group consisting of C₁₋₂₀-alkyl,        C₅₋₆-cycloalkyl, phenyl, 5 to 9 membered heteroaryl,    -   wherein at least one CH₂-group, but not adjacent CH₂-groups, of        C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl and        substituted C₅₋₈-cycloalkyl, can be replaced by the linking        group O.

In even most preferred compounds of formula (1)

X is S,

R¹ is selected from the group consisting of C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substitutedC₅₋₈-cycloalkenyl,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each otherselected from the group consisting of H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₅₋₈-cycloalkyl, and substituted C₅₋₈-cycloalkyl,

-   -   wherein    -   substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each        occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which        are substituted with at least one substituent independently        selected from the group consisting of C₅₋₆-cycloalkyl, phenyl        and 5 to 9 membered heteroaryl,    -   substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, phenyl and 5 to 9 membered        heteroaryl.

In particular preferred compounds of formula (1)

X is S,

R¹ is selected from the group consisting of C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl and substitutedC₅₋₈-cycloalkenyl,R², R⁴, R⁵, R⁶, R⁷ and R⁹ are H, and R³ and R⁸ are independently fromeach other selected from the group consisting of H, C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl and substitutedC₅₋₈-cycloalkyl,

-   -   wherein    -   substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each        occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which        are substituted with at least one substituent independently        selected from the group consisting of C₅₋₆-cycloalkyl and        phenyl, substituted C₅₋₈-cycloalkyl and substituted        C₅₋₈-cycloalkenyl, at each occurrence, are C₅₋₈-cycloalkyl,        respectively, C₅₋₈-cycloalkenyl, which are substituted with at        least one substituent independently selected from the group        consisting of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl and phenyl.

Also part of the present invention is a process for the preparation ofthe compounds of formula

wherein

X is O, S or NR¹⁰,

-   -   wherein R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,        substituted C₂₋₃₀-alkynyl or C(O)—OR¹¹,        R¹ and R¹¹ are independently from each other selected from the        group consisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,        substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substituted        C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl, and substituted        C₅₋₈-cycloalkenyl,        R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each        other selected from the group 5 consisting of H, C₁₋₃₀-alkyl,        substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,        C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,        substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted        O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl, substituted S—C₁₋₃₀-alkyl,        C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15 membered heteroaryl,        substituted 5 to 15 membered heteroaryl and halogen; or R² and        R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹        together with the C-atoms, to which they are connected, form a 6        to 10 membered aromatic ring system, substituted 6 to 10        membered aromatic ring system, 5 to 12 membered heteroaromatic        ring system or a substituted 5 to 12 membered heteroaromatic        ring system,    -   wherein    -   substituted C₁₋₃₀-alkyl, substituted C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkynyl, substituted O—C₁₋₃₀-alkyl and substituted        S—C₁₋₃₀-alkyl, at each occurrence, are C₁₋₃₀-alkyl,        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, O—C₁₋₃₀-alkyl, respectively,        S—C₁₋₃₀-alkyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,        OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),        C(O)—R^(a), C(O)OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;    -   substituted C₅₋₈-cycloalkyl, and substituted C₅₋₈-cycloalkenyl,        at each occurrence, are C₅₋₈-cycloalkyl, respectively,        C₅₋₈-cycloalkenyl, which are substituted with at least one        substituent independently selected from the group consisting of        C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl,        C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a), OC(O)—R^(a),        OC(O)OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),        C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂;    -   substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,        substituted 6 to 10 membered aromatic ring system, and        substituted 5 to 12 membered heteroaromatic ring system, at each        occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10        membered aromatic ring system, respectively, 5 to 12 membered        heteroaromatic ring system, which are substituted with at least        one substituent independently selected from the group consisting        of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl,        C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,        OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),        C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),        C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),        C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),        NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b),        NR^(a)—C(O)—OR^(b), NR^(a)C(O)—NR^(b)R^(c), SR^(a),        S—C(O)—R^(a), halogen, CN, and NO₂,        wherein at least one CH₂-group, but not adjacent CH₂-groups, of        C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted        C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,        C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,        substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted        O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, can        be replaced by a linking group selected from the group        consisting of O, S, NR¹², CO, O—C(O), C(O)—O, O—C(O)—O, S—C(O),        C(O)—S, NR¹²—C(O), C(O)—NR¹², OC(O)—NR¹² and NR¹²—C(O)O,    -   wherein    -   R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,        substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted        C₂₋₃₀-alkynyl or C(O)—OR^(d),    -   R^(a), R^(b), R^(c) and R^(d) are independently from each other        and at each occurrence selected from the group consisting of H,        C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl,        C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, and 5 to 12 membered heteroaryl,        which process comprises the step of treating a compound of        formula

wherein X, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the meaning asindicated for the compound of formula (1)with

R¹O—C(O)-LG

wherein R¹ has the meaning as indicated for the compound of formula (1),and LG is a leaving groupin order to obtain a compound of formula (1).

The leaving group LG can be —O—C(O)—OR¹, wherein R¹ has the meaning asindicated for the compound of formula (1), or

The reaction is usually performed at ambient temperatures. The reactionis usually performed in a suitable organic solvent such as THF.

If R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are all H, and X is S, the compoundof formula (2) has formula

and can be prepared by treating o-aminothiophenol withdichloromaleimide. The reaction is usually performed at elevatedtemperatures, such as at a temperature in the range of 80 to 150° C.,and in the presence of acetic acid.

If X is S, the compound of formula (2) has formula

whereinR², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the meaning as indicated for thecompound of formula (2),and can be prepared by treating a compound of formula

wherein R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ have the meaning as indicatedfor the compound of formula (2),with dichloromaleimide.

The reaction is usually performed at elevated temperatures, such as at atemperature in the range of 80 to 180° C., and in the presence of aceticacid.

If R⁹═R², R⁸═R³, R⁷═R⁴ and R⁶═R⁵, the compound of formula (3) hasformula

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2), and can be prepared by treating a compound of

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2) with zinc.

The reaction is usually performed at elevated temperatures, such as at atemperature in the range of 40 to 80° C., and in the presence of an acidsuch as HCl or acetic acid.

A compound of formula

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2), can be prepared by heating a compound of formula

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2), The reaction is usually performed at elevatedtemperatures, such as at a temperature in the range of 160 to 260° C.

The compound of formula

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2), can be prepared by treating a compound of formula

with N,N-dimethylthiocarbamoyl chloride.

The reaction is usually performed in the presence of a base. An examplesof a base is 1,4-diazabicyclo[2.2.2]octane (DABCO). The reaction isusually performed at elevated temperatures, such as at a temperature inthe range of 50 to 120° C. The reaction is usually performed in asuitable organic solvent such as DMF.

The compound of formula

can be prepared by treating a compound of formula

wherein R², R³, R⁴ and R⁵ have the meaning as indicated for the compoundof formula (2), nitric acid.

The reaction is usually performed at a temperature in the range of 10 to20° C. The reaction is usually performed in the presence of an acid suchas acetic acid.

Also part of the invention is an electronic device comprising thecompounds of the present invention.

The electronic device can be an organic photovoltaic device (OPVs), anorganic field-effect transistor (OFETs), an organic light emitting diode(OLEDs) or an organic photodiode (OPDs).

Preferably, the electronic device is an organic photovoltaic device(OPVs), an organic field-effect transistor (OFETs) or an organicphotodiode (OPDs).

More preferably, the electronic device is an organic field effecttransistor (OFET).

Usually, an organic field effect transistor comprises a dielectriclayer, a semiconducting layer and a substrate. In addition, an organicfield effect transistor usually comprises a gate electrode andsource/drain electrodes.

Preferably, the semiconducting layer comprises the compounds of thepresent invention. The semiconducting layer can have a thickness of 5 to500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.

The dielectric layer comprises a dielectric material. The dielectricmaterial can be silicon dioxide or aluminium oxide, or, an organicpolymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA),poly(4-vinylphenol) (PVP), poly(vinyl alcohol) (PVA), benzocyclobutene(BCB), or polyimide (PI). The dielectric layer can have a thickness of10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to800 nm.

The dielectric layer can in addition to the dielectric material comprisea self-assembled monolayer of organic silane derivates or organicphosphoric acid derivatives. An example of an organic silane derivativeis octyltrichlorosilane. An examples of an organic phosphoric acidderivative is decylphosphoric acid. The self-assembled monolayercomprised in the dielectric layer is usually in contact with thesemiconducting layer.

The source/drain electrodes can be made from any suitable organic orinorganic source/drain material. Examples of inorganic source/drainmaterials are gold (Au), silver (Ag) or copper (Cu), as well as alloyscomprising at least one of these metals. The source/drain electrodes canhave a thickness of 1 to 100 nm, preferably from 20 to 70 nm.

The gate electrode can be made from any suitable gate material such ashighly doped silicon, aluminium (Al), tungsten (W), indium tin oxide orgold (Au), or alloys comprising at least one of these metals. The gateelectrode can have a thickness of 1 to 200 nm, preferably from 5 to 100nm.

The substrate can be any suitable substrate such as glass, or a plasticsubstrate such as polyethersulfone, polycarbonate, polysulfone,polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).Depending on the design of the organic field effect transistor, the gateelectrode, for example highly doped silicon can also function assubstrate.

The organic field effect transistor can be prepared by methods known inthe art.

For example, a bottom-gate top-contact organic field effect transistorcan be prepared as follows: The dielectric material, for example Al₂O₃or silicon dioxide, can be applied as a layer on a gate electrode suchas highly doped silicon wafer, which also functions as substrate, by asuitable deposition method such as atom layer deposition (ALD) orthermal evaporation. A self-assembled monolayer of an organic phosphoricacid derivative or an organic silane derivative can be applied to thelayer of the dielectric material. For example, the organic phosphoricacid derivative or the organic silane derivative can be applied fromsolution using solution-deposition techniques. The semiconducting layercan be formed by either solution deposition or thermal evaporation invacuo of the compounds of the present invention on the self-assembledmonolayer of the organic phosphoric acid derivative or the organicsilane derivative. Source/drain electrodes can be formed by depositionof a suitable source/drain material, for example tantalum (Ta) and/orgold (Au), on the semiconducting layer through a shadow masks. Thechannel width (W) is typically 500 μm and the channel length (L) istypically 100 μm.

For example, a top-gate bottom-contact organic field effect transistorcan be prepared as follows: Source/drain electrodes can be formed byevaporating a suitable source/drain material, for example gold (Au), onphoto-lithographically defined electrodes on a suitable substrate, forexample a glass substrate. The semiconducting layer can be formed bydepositing a solution of the compounds of the present invention, forexample by spin-coating, on the source/drain electrodes, followed byannealing the layer at elevated temperatures such as at a temperature inthe range of 80 to 360° C. After quenching the semiconducting layer, adielectric layer can be formed by applying, for example, byspin-coating, a solution of a suitable dielectric material such aspoly(methylmethacryate), on the semiconducting layer. The gate electrodeof a suitable source/drain material, for example gold (Au), can beevaporated through a shadow mask on the dielectric layer.

Also part of the invention is the use of the compounds of the presentinvention as semiconducting material.

The compounds of the present invention show high solubility in organicsolvents, such as toluene, DMF, THF, chlorobenzene and CHCl₃, and arethus compatible with liquid processing techniques. At the same time, thecompounds of the present invention, when applied as a layer in anorganic electronic device, yield organic electronic devices showing goodperformance such as high charge carrier mobilities, preferably of above5.0×10⁻³ cm² V⁻¹s⁻¹.

In addition, the compounds of the present invention also show highstability towards oxidation by air.

FIG. 1 shows the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1a as semiconductingmaterial at a gate voltage V_(GS) of −11 V, −10 V, −9 V and −8 V.

FIG. 2 shows the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 14 comprising compound 1a as semiconducting material at adrain-source voltage V_(DS) of −5 V.

FIG. 3 shows the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1b as semiconductingmaterial at a gate voltage V_(GS) of −11 V, −10 V, −9 V and −7 V.

FIG. 4 shows the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 14 comprising compound 1b as semiconducting material at adrain-source voltage V_(DS) of −5 V.

FIG. 5 shows the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1e as semiconductingmaterial at a gate voltage V_(GS) of −10 V, −8 V and −6 V.

FIG. 6 shows the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 14 comprising compound 1e as semiconducting material at adrain-source voltage V_(DS) of −5 V.

FIG. 7 shows the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1g as semiconductingmaterial at a gate voltage V_(GS) of −10 V, −9 V and −8 V.

FIG. 8 shows the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 14 comprising compound 1g as semiconducting material at adrain-source voltage V_(DS) of −5 V.

FIG. 9 shows the drain-source current I_(DS) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 16 comprising compound 1b as semiconductingmaterial at a gate voltage V_(GS) of −80 V, −60 V, −40 V, −20 V and 0 V.

FIG. 10 shows the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 16 comprising compound 1b as semiconducting material at adrain-source voltage V_(DS) of −80 V.

EXAMPLES Example 1 Preparation of Compound 1a

Preparation of Compound 2a

0.83 g (5 mmol) of dichloromaleimide and 1.25 g (10 mmol) ofo-aminothiophenol were added to 30 ml of acetic acid, and stirred at120° C. for 6 hours under N₂. After cooling to r.t., the precipitate wasisolated by filtration, washed with methanol and THF. Compound 2a (1.26g) was used in the next step without further purification.

Preparation of Compound 1a

215 mg (0.7 mmol) of compound 2a, 13 mg (0.1 mmol) of4-dimethylaminopyridine, and 458 mg (2.1 mmol) of di-tert-butyldicarbonate were added to 10 ml of THF, and stirred at r.t. overnightunder N₂. The precipitate was isolated with filtration, washed withtert-butylmethylether, yielding 232 mg (0.57 mmol; 81%) of compound 1aas an orange solid. ¹H-NMR spectrum (CDCl₃). δ [ppm] 1.72 (s, 9H), 7.15(t, 2H), 7.21-7.28 (m, 4H), 7.50 (d, 2H).

Example 2 Preparation of Compound 1b

Preparation of Compound 6a

To a solution of 9.85 g (60 mmol) of 4-pentylphenol in 70 ml of aceticacid was added 7.6 g of nitric acid dissolved in 20 ml of acetic aciddropwise with keeping the temperature in the range of 10-15° C. Thereaction mixture was stirred at r.t. for 4 hours, and then poured towater and extracted with ethyl acetate. The organic phase was washedwith NaHCO₃aq and water, dried over MgSO₄, and concentrated. Compound 6awas used in the next step without further purification.

Preparation of Compound 5a

To a solution of 10.5 g (50 mmol) of compound 6a, 15.1 g (135 mmol) ofDABCO in 50 ml of DMF was added 7.73 g (63 mmol) ofN,N-dimethylthiocarbamoyl chloride by portions. The reaction mixture wasstirred at 70° C. for 3 hours, and then poured to water and acidifiedwith 6N HCl. Compound 5a was extracted with ethyl acetate, washed withwater, dried over MgSO₄, and concentrated. The residue is purified byflash chromatography on silica gel with hexane and CH₂Cl₂ (1:1) aseluent, yielding 13.0 g (44 mmol; 88%) of compound 5a as a brown liquid.¹H-NMR (CDCl₃). δ [ppm]: 0.90 (t, 3H), 1.25-1.38 (m, 4H), 1.62-1.70 (m,2H), 2.69 (t, 2H), 3.39 (s, 3H), 3.46 (s, 3H), 7.15 (d, 1H), 7.46 (d,1H), 7.92 (s, 1H).

Preparation of Compound 4a

12.7 g (43 mmol) of compound 5a was placed in a reaction vessel andheated at 210° C. with stirred under N₂ for 3 hours. After cooling tor.t., 80 ml of THF was added. To the solution was added 5.31 g (95 mmol)of potassium hydroxide dissolved in 20 ml of methanol dropwise withcooled by an ice bath. The reaction mixture was stirred at r.t. for 30min, and poured to ice, acidified with conc. HCl. Compound 4a wasextracted with ethyl acetate, washed with water, dried over MgSO₄, andconcentrated. ¹H-NMR spectrum (CDCl₃). δ [ppm]: 0.89 (t, 3H), 1.25-1.37(m, 4H), 1.55-1.65 (m, 2H), 2.63 (t, 2H), 3.96 (s, 1H), 7.25 (d, 1H),7.33 (d, 1H), 8.06 (s, 1H).

Preparation of Compound 3a

To a solution of 5.15 g (23 mmol) of compound 4a in 9 ml of conc HCl and170 ml of acetic acid was added 18.0 g (275 mmol) of zinc by portions at60° C. The reaction mixture was stirred at 60° C. overnight. Aftercooling to r.t., insoluble solid was removed by filtration. The filtratewas concentrated by a rotary evaporator and water was added to theresidue, yielding a precipitate.

The precipitate was isolated by filtration, washed with ethanol.Compound 3b was obtained with a yield of 5.16 g (11 mmol; 99%) as awhite solid. ¹H-NMR spectrum (DMSO-d₆). δ [ppm]: 0.83 (t, 6H), 1.18-1.32(m, 8H), 1.42-1.53 (m, 4H), 2.39 (t, 4H), 5.72 (br s, 4H), 6.63 (d, 2H),6.83 (s, 2H), 7.18 (d, 2H).

Preparation of Compound 2b

To 300 ml of acetic acid 7.26 g (16 mmol) of compound 3a and 2.66 g (16mmol) of 3,4-dichloromaleimide were added and stirred at 140° C.overnight. After removing the solvent by a rotary evaporator, theresidue was suspended in water. The solid was isolated by filtration,washed with methanol. Compound 2b was obtained as an orange solid.Compound 2b was used in the next step without further purification.

Preparation of Compound 1b

To 30 ml of THF 1.34 g (3 mmol) of compound 2b, 55 mg (0.45 mmol) of4-dimethylaminopyridine, and 1.96 g (9 mmol) of di-tert-butyldicarbonate were added, and stirred at r.t. overnight under N₂. Theproduct was extracted with CH₂Cl₂, washed with water, dried over MgSO₄,and concentrated. The residue was purified by recrystallization fromethyl acetate and hexane (1:1) solution, yielding 1.06 g (1.9 mmol; 65%)of compound 1b as an orange solid. ¹H-NMR (CDCl₃). δ [ppm]: 0.89 (t,6H), 1.28-1.39 (m, 8H), 1.57-1.68 (m, 4H), 1.72 (s, 9H), 2.59 (t, 4H),6.98 (d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).

Example 3 Preparation of Compound 1c

Compound 1c is prepared in analogy to compound 1b in example 2, startingfrom 4-heptylphenol instead of from 4-pentylphenol, and is obtained asan orange solid. ¹H-NMR spectrum (CDCl₃) δ [ppm]: 0.88 (t, 6H),1.20-1.38 (m, 16H), 1.55-1.63 (m, 4H), 1.71 (s, 9H), 2.59 (t, 4H), 6.98(d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).

Example 4 Preparation of Compound 1d

Compound 1d is prepared in analogy to compound 1b in example 2, startingfrom 4-dodecylphenol instead of from 4-pentylphenol, and is obtained asan orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]: 0.88 (t, 6H),1.21-1.36 (m, 36H), 1.53-1.63 (m, 4H), 1.72 (s, 9H), 2.58 (t, 4H), 6.98(d, 2H), 7.11 (d, 2H), 7.32 (s, 2H).

Example 5 Preparation of Compound

Compound 1e is prepared in analogy to compound 1b in example 2, startingfrom 4-tetradecylphenol instead of from 4-pentylphenol, and is obtainedas an orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]: 0.87 (t, 6H),1.20-1.33 (m, 44H), 1.60-1.70 (m, 4H), 1.72 (s, 9H), 2.59 (t, 4H), 6.98(d, 2H), 7.12 (d, 2H), 7.33 (s, 2H).

Example 6 Preparation of Compound 1f

Compound 1f is prepared in analogy to compound 1b in example 2, startingfrom 4-docosyl-phenol instead of from 4-pentylphenol, and is obtained asan orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]: 0.86 (t, 6H),1.20-1.35 (m, 76H), 1.56-1.63 (m, 4H), 1.72 (s, 9H), 2.58 (t, 4H), 6.98(d, 2H), 7.12 (d, 2H), 7.32 (s, 2H).

Example 7 Preparation of Compound 1g

Compound 1g is prepared in analogy to compound 1b in example 2, startingfrom 4-[4-pentylcyclohexyl)-phenol instead of from 4-pentylphenol, andis obtained as an orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]: 0.89(t, 6H), 0.98-1.10 (m, 4H), 1.18-1.38 (m, 18H), 1.38-1.52 (m, 4H), 1.72(s, 9H), 1.83-1.92 (m, 8H), 2.40-2.49 (m, 2H), 7.02 (d, 2H), 7.12 (d,2H), 7.35 (s, 2H).

Example 8 Preparation of Compound 1h

Compound 1h is prepared in analogy to compound 1b in example 2, startingfrom 4-dodecylphenol instead of from 4-pentylphenol, and is obtained asan orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]: 0.85 (t, 3H),1.21-1.37 (m, 18H), 1.60-1.68 (m, 11H), 2.67 (t, 2H), 7.22 (d, 1H), 7.29(d, 1H), 7.36-7.48 (m, 5H), 7.61-7.67 (m, 3H), 7.75 (s, 1H).

Example 9 Preparation of Compound 1i

Compound 1i is prepared in analogy to compound 1b in example 2, usingdi-(2-methyl-sec-butyl) dicarbonate instead of di-tert-butyldicarbonate, and is obtained as an orange solid. ¹H-NMR spectrum (CDCl₃)d [ppm]: 0.89 (t, 6H), 1.12 (t, 3H), 1.25-1.38 (m, 8H), 1.55-1.64 (m,4H), 1.70 (s, 6H), 1.99 (q, 2H), 2.59 (t, 4H), 6.98 (d, 2H), 7.11 (d,2H), 7.33 (s, 2H).

Example 10 Preparation of Compound 1j

Compound 1j is prepared in analogy to compound 1b in example 2, usingdi-(1-methylcyclohexyl) dicarbonate instead of di-tert-butyldicarbonate, and is obtained as an orange solid. ¹H-NMR spectrum (CDCl₃)d [ppm]: 0.80-0.95 (m, 6H), 1.10-1.65 (m, 21H), 1.95-2.08 (m, 2H),2.40-2.49 (m, 2H), 2.58 (t, 4H), 6.98 (d, 2H), 7.12 (d, 2H), 7.34 (s,2H).

Example 11 Preparation of Compound 1k

Compound 1k is prepared in analogy to compound 1b in example 2, usingdi-(1-ethyl-1,5-dimethyl-hexyl) dicarbonate instead of di-tert-butyldicarbonate, and is obtained as an orange solid. ¹H-NMR spectrum (CDCl₃)d [ppm]: 0.86-0.91 (m, 12H), 1.07 (t, 3H), 1.20-1.37 (m, 12H), 1.47-1.67(m, 8H), 1.85-2.13 (m, 4H), 2.58 (t, 4H), 6.97 (d, 2H), 7.11 (d, 2H),7.32 (s, 2H).

Example 12 Preparation of Compound 1l

Compound 11 is prepared in analogy to compound 1b in example 2, usingdi-(1-isopropyl-4-methyl-cyclohex-3-en-1-yl) dicarbonate instead ofdi-tert-butyl dicarbonate, and is obtained as an orange solid. ¹H-NMRspectrum (CDCl₃) d [ppm]: 0.80-1.72 (m, 27H), 1.75-1.87 (m, 1H),1.92-2.03 (m, 1H), 2.27-2.45 (m, 2H), 2.58 (t, 4H), 2.65-2.79 (m, 1H),2.92-3.02 (m, 1H), 5.32 (s, 1H), 6.97 (d, 2H), 7.12 (d, 2H), 7.29 (s,2H).

Example 13 Preparation of Compound 1m

Compound 1m is prepared in analogy to compound 1b in example 2, usingdi-(1,1-dimethylallyl) dicarbonate instead of di-tert-butyl dicarbonate,and is obtained as an orange solid. ¹H-NMR spectrum (CDCl₃) d [ppm]:0.82-0.95 (m, 6H), 1.20-1.40 (m, 12H), 1.52-1.67 (m, 4H), 1.79 (s, 6H),2.59 (t, 4H), 5.23 (d, 1H), 5.51 (d, 1H), 6.28 (dd, 1H), 6.98 (d, 2H),7.11 (d, 2H), 7.33 (s, 2H).

Example 14 Preparation of Field-Effect Transistors Comprising Compounds1a, 1b, 1e, Respectively, 1g as Semiconducting Material

30 nm ALD Al₂O₃ coated, highly doped silicon wafers were thoroughlycleaned with acetone and isopropanol and after a short oxygen plasmatreatment treated with a solution of decyl-phosphonic acid inisopropanol. The compound 1a, 1b, 1e, respectively, 1g was thermallyevaporated in high vacuum (<10⁻⁵ mbar). A 50 nm-thick of Au layer forsource and drain electrodes was deposited though a shadow mask to givetop contact OFET devices. The channel width (W) was 500 μm and channellength (L) was 100 μm.

All electrical measurements were performed in ambient air in the darkusing a B1500 Agilent parameter analyzer.

In FIG. 1 the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1a as semiconductingmaterial at a gate voltage V_(GS) Of −11 V, −10 V, −9 V and −8 V isshown.

In FIG. 2 the drain-source current I_(DS) in relation to the gate-sourcevoltage V_(GS) (transfer curve) for field effect transistor of example14 comprising compound 1a as semiconducting material at a drain-sourcevoltage V_(DS) of −5 V is shown.

In FIG. 3 the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1b as semiconductingmaterial at a gate voltage V_(GS) Of −11 V, −10 V, −9 V and −7 V isshown.

In FIG. 4 the drain-source current I_(DS) in relation to the gate-sourcevoltage V_(GS) (transfer curve) for field effect transistor of example14 comprising compound 1b as semiconducting material at a drain-sourcevoltage V_(DS) of −5 V is shown.

In FIG. 5 the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1e as semiconductingmaterial at a gate voltage V_(GS) of −10 V, −8 V and −6 V is shown.

In FIG. 6 the drain-source current I_(DS) in relation to the gate-sourcevoltage V_(GS) (transfer curve) for field effect transistor of example14 comprising compound 1e as semiconducting material at a drain-sourcevoltage V_(DS) of −5 V is shown.

In FIG. 7 the drain-source current I_(ds) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 14 comprising compound 1g as semiconductingmaterial at a gate voltage V_(GS) of −10 V, −9 V and −8 V is shown.

In FIG. 8 the drain-source current I_(DS) in relation to the gate-sourcevoltage V_(GS) (transfer curve) for field effect transistor of example14 comprising compound 1g as semiconducting material at a drain-sourcevoltage V_(DS) of −5 V is shown.

The field effect transistors comprising 1a, 1b, 1e, respectively, 1gshowed typical p-type characteristics.

The charge-carrier mobility (μ) was extracted in the saturation regimefrom the slope of (I_(DS))^(1/2) versus V_(GS) using the equationp=2L/(W*C_(i))*(dl_(DS) ^(1/2)/dV_(GS))², wherein L is the channellength, W is the channel width, C_(i) is the capacitance per unit areaof the dielectric layer, I_(DS) is the drain-source current, and V_(GS)is the gate-source voltage.

The threshold voltage (V_(th)) was extracted from the intersection ofthe linear extrapolation of the I_(DS) ^(1/2) versus V_(GS) plot withthe V_(GS) axis.

The results are depicted in table 1

TABLE 1 Compound V_(th) [V] μ [cm²/Vs] I_(on/off) 1a −6.9 0.13 1E4 1b−4.5 0.68 7E4 1e −3.9 0.23 2E6 1g −6.5 0.008 4E4

Example 15

The Solubility of the Compounds 1a, 1b, 1c and 1d at 25° C. wereCompared to the Solubility of the Compound of Formula

The results are outlined in table 2

TABLE 2 Compound DMF THF clorobenzene CHCl₃ 2a (comparative) <1 mg/mL <1mg/mL <1 mg/mL <1 mg/mL 1a 1 to 5 mg/mL 1 to 5 mg/mL 5 to 10 mg/mL 5 to10 mg/mL 1b <1 mg/mL >10 mg/mL >10 mg/mL >10 mg/mL 1c <1 mg/mL >10mg/mL >10 mg/mL >10 mg/mL 1d >10 mg/mL >10 mg/mL >10 mg/mL >10 mg/mL

Example 16 Preparation of Field-Effect Transistors Comprising Compound1b as Semiconducting Material

SiO₂/Si substrates were thoroughly cleaned with piranha solution,ultrapure water, followed by isopropanol, and the substrates werefunctionalized with octadecyltrichlorosilane (OTS) from solution. A thinfilm of compound 1b was formed on the OTS-treated SiO₂/Si substrate byspin coating a 5 mg/ml solution of compound 1b in CHCl₃ at 4000 rpm for30 sec, and annealed at 200° C. for 10 min on a hot-plate. On top of theorganic thin film, Au layer was deposited through a shadow mask assource and drain electrodes to give top contact OFET devices. Thechannel width (W) was 3 mm and channel length (L) was 50 μm.

All electrical measurements are performed in ambient air in the darkusing a Keithley 4200 parameter analyzer.

In FIG. 9 the drain-source current I_(DS) in relation to thedrain-source voltage V_(DS) (output curve) for the field effecttransistor of example 16 comprising compound 1b as semiconductingmaterial at a gate voltage V_(GS) of −80 V, −60 V, −40 V, −20 V and 0 Vis shown.

In FIG. 10 the drain-source current I_(DS) in relation to thegate-source voltage V_(GS) (transfer curve) for field effect transistorof example 16 comprising compound 1b as semiconducting material at adrain-source voltage V_(DS) of −80 V is shown.

The field effect transistors comprising 1b showed typical p-typecharacteristics.

To record the transfer curve the drain-source voltage (V_(DS)) was heldto −80 V. The charge-carrier mobility (p) was extracted in thesaturation regime from the slope of (I_(DS))^(1/2) versus V_(GS) usingthe equation p=2L/(W*C_(i))*(dl_(DS) ^(1/2)/dV_(GS))², wherein L is thechannel length, W is the channel width, C_(i) is the capacitance perunit area of the dielectric layer, I_(DS) is the drain-source current,and V_(GS) is the gate-source voltage.

The threshold voltage (V_(th)) was extracted from the intersection ofthe linear extrapolation of the I_(DS) ^(1/2) versus V_(GS) plot withthe V_(GS) axis.

The results are depicted in table 3

TABLE 3 Compound V_(th)/V μ/cm²/Vs I_(on/off) Compound 1b −9.0 0.022 3E5

1: A compound of formula (1):

wherein: X is O, S or NR¹⁰, R¹⁰ is H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₂₋₃₀-alkynyl or C(O)—OR¹¹, R¹ and R¹¹ are independentlyfrom each other selected from the group consisting of C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl,C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substitutedC₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl, and substituted C₅₋₈-cycloalkenyl,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each otherselected from the group consisting of H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl, substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl,substituted O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl, substituted S—C₁₋₃₀-alkyl,C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15 membered heteroaryl,substituted 5 to 15 membered heteroaryl and halogen, or R² and R³, R³and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹ together with theC-atoms, to which they are connected, form a 6 to 10 membered aromaticring system, substituted 6 to 10 membered aromatic ring system, 5 to 12membered heteroaromatic ring system or a substituted 5 to 12 memberedheteroaromatic ring system, substituted C₁₋₃₀-alkyl, substitutedC₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkynyl, substituted O—C₁₋₃₀-alkyl andsubstituted S—C₁₋₃₀-alkyl, at each occurrence, are C₁₋₃₀-alkyl,C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, O—C₁₋₃₀-alkyl, respectively,S—C₁₋₃₀-alkyl, which are substituted with at least one substituentindependently selected from the group consisting of C₅₋₆-cycloalkyl,C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a), OC(O)—R^(a),OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₅₋₈-cycloalkyl, and substituted C₅₋₈-cycloalkenyl, at eachoccurrence, are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a),OC(O)—R^(a), OC(O)OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,substituted 6 to 10 membered aromatic ring system, and substituted 5 to12 membered heteroaromatic ring system, at each occurrence, areC₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ringsystem, respectively, 5 to 12 membered heteroaromatic ring system, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, 5 to 12 memberedheteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c),C(O)—NR^(a)—OR^(b), C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b),C(O)—SR^(a), NR^(a)R^(b), NR^(a)—NR^(b)R, NR^(a)—C(O)R^(b),NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a),halogen, CN, and NO₂, at least one CH₂-group, but not adjacentCH₂-groups, of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted O—C₁₋₃₀-alkyl,S—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, can be replaced by alinking group selected from the group consisting of O, S, NR¹², CO,O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR¹²—C(O), C(O)—NR¹²,OC(O)—NR¹² and NR¹²—C(O)—O, R¹² is H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₂₋₃₀-alkynyl or C(O)—OR^(d), and R^(a), R^(b), R^(c) andR^(d) are independently from each other and at each occurrence selectedfrom the group consisting of H, C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl,C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, and 5 to12 membered heteroaryl. 2: The compound of formula (1) of claim 1,wherein: X is O, S or NR, R¹⁰ is H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl or C(O)—OR¹¹, R¹and R¹¹ are independently from each other selected from the groupconsisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸ and R⁹ are independently from each other selected from the groupconsisting of H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl,substituted O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl, substituted S—C₁₋₃₀-alkyl,C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15 membered heteroaryl,substituted 5 to 15 membered heteroaryl and halogen; or R² and R³, R³and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹ together with theC-atoms, to which they are connected, form a 6 to 10 membered aromaticring system, substituted 6 to 10 membered aromatic ring system, 5 to 12membered heteroaromatic ring system or a substituted 5 to 12 memberedheteroaromatic ring system, substituted C₁₋₃₀-alkyl, substitutedC₂₋₃₀-alkenyl, substituted O—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl,at each occurrence, are C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, O—C₁₋₃₀-alkyl,respectively, S—C₁₋₃₀-alkyl, which are substituted with at least onesubstituent independently selected from the group consisting ofC₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a),OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R, NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl, at eachoccurrence, are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5to 12 membered heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b), C(O)—NR^(a)—C(O)—R^(b),C(O)NR^(a)—C(O)—OR^(b), C(O)—SR^(a), NR^(a)R^(b), NR^(a)—NR^(b)R,NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),S—C(O)—R^(a), halogen, CN, and NO₂; substituted C₆₋₁₄-aryl, substituted5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ringsystem and substituted 5 to 12 membered heteroaromatic ring system, ateach occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10membered aromatic ring system, respectively, 5 to 12 memberedheteroaromatic ring system, which are substituted with at least onesubstituent independently selected from the group consisting ofC₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,OR^(a), OC(O)—R^(a), OC(O)OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a),C(O)—OR^(a), C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R, C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂, atleast one CH₂-group, but not adjacent CH₂-groups, of C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl,C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl andsubstituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted O—C₁₋₃₀-alkyl,S—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, can be replaced by alinking group selected from the group consisting of O, S, NR¹², CO,O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR¹²—C(O), C(O)—NR¹²,OC(O)—NR¹² and NR¹²—C(O)—O, R¹² is H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, or C(O)—OR^(d), and R^(a), R^(b), R^(c) and R^(d) areindependently from each other and at each occurrence selected from thegroup consisting of H, C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5to 12 membered heteroaryl. 3: The compound of claim 1, wherein: X is O,S or NR¹⁰, R¹⁰ is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or C(O)—OR¹¹,R¹ and R¹¹ are independently from each other selected from the groupconsisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸ and R⁹ are independently from each other selected from the groupconsisting of H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15membered heteroaryl and substituted 5 to 15 membered heteroaryl; or R²and R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹together with the C-atoms, to which they are connected, form a 6 to 10membered aromatic ring system, substituted 6 to 10 membered aromaticring system, 5 to 12 membered heteroaromatic ring system or asubstituted 5 to 12 membered heteroaromatic ring system, substitutedC₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each occurrence, areC₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which are substituted with atleast one substituent independently selected from the group consistingof C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a),OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)Re, C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R, NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R, SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl, at eachoccurrence, are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5to 12 membered heteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a),OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b),C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b), C(O)—NR^(a)—C(O)—R^(b),C(O)NR^(a)—C(O)—OR^(b), C(O)—SR^(a), NR^(a)R^(b), NR^(a)—NR^(b)R,NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a),S—C(O)—R^(a), halogen, CN, and NO₂; substituted C₆₋₁₄-aryl, substituted5 to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ringsystem, and substituted 5 to 12 membered heteroaromatic ring system, ateach occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10membered aromatic ring system, respectively, 5 to 12 memberedheteroaromatic ring system, which are substituted with at least onesubstituent independently selected from the group consisting ofC₁₋₁₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl,OR^(a), OC(O)—R^(a), OC(O)OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a),C(O)—OR^(a), C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R, C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂, atleast one CH₂-group, but not adjacent CH₂-groups, of C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl,C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl C₅₋₈-cycloalkenyl andsubstituted C₅₋₈-cycloalkenyl can be replaced by a linking groupselected from the group consisting of O, S, NR¹², CO, O—C(O), C(O)—O,O—C(O)—O, S—C(O), C(O)—S, NR¹²—C(O), C(O)—NR¹², OC(O)—NR¹² andNR¹²—C(O)—O, R¹² is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl orC(O)—OR^(d), R^(a), R^(b), R^(c) and R^(d) are independently from eachother and at each occurrence selected from the group consisting of H,C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5 to 12 memberedheteroaryl. 4: The compound of claim 1, wherein: X is O, S or NR¹⁰, R¹⁰is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or C(O)—OR¹¹, R¹ and R¹¹ areindependently from each other selected from the group consisting ofC₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substitutedC₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸ and R⁹ are independently from each other selected from the groupconsisting of H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15membered heteroaryl and substituted 5 to 15 membered heteroaryl; or R²and R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹together with the C-atoms, to which they are connected, form a 6 to 10membered aromatic ring system, substituted 6 to 10 membered aromaticring system, 5 to 12 membered heteroaromatic ring system or asubstituted 5 to 12 membered heteroaromatic ring system, substitutedC₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl, at each occurrence, areC₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, which are substituted with atleast one substituent independently selected from the group consistingof C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, and 5 to 12 membered heteroaryl,substituted C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl, at eachoccurrence, are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl,and 5 to 12 membered heteroaryl; substituted C₆₋₁₄-aryl, substituted 5to 15 membered heteroaryl, substituted 6 to 10 membered aromatic ringsystem, and substituted 5 to 12 membered heteroaromatic ring system, ateach occurrence, are C₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10membered aromatic ring system, respectively, 5 to 12 memberedheteroaromatic ring system, which are substituted with at least onesubstituent independently selected from the group consisting ofC₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl;wherein at least one CH₂-group, but not adjacent CH₂-groups, ofC₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substitutedC₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl can be replaced by alinking group selected from the group consisting of O, S, and NR¹², R¹²is H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl or C(O)—OR^(d), and R^(d) isat each occurrence selected from the group consisting of H, C₁₋₂₀-alkyl,C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl,C₆₋₁₀-aryl, and 5 to 12 membered heteroaryl. 5: The compound of claim 1,wherein: X is S, R¹ is selected from the group consisting ofC₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substitutedC₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, R², R³, R⁴, R⁵, R⁶,R⁷, R⁸ and R⁹ are independently from each other selected from the groupconsisting of H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl,substituted C₅₋₈-cycloalkyl, C₆₋₁₀-aryl, substituted C₆₋₁₀-aryl, 5 to 12membered heteroaryl, and substituted 5 to 12 membered heteroaryl; or R²and R³, R³ and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹together with the C-atoms, to which they are connected, form a 6membered aromatic ring system, substituted 6 membered aromatic ringsystem, 5 to 9 membered heteroaromatic ring system or a substituted 5 to9 membered heteroaromatic ring system, substituted C₁₋₃₀-alkyl andsubstituted C₂₋₃₀-alkenyl, at each occurrence, are C₁₋₃₀-alkyl,respectively, C₂₋₃₀-alkenyl, which are substituted with at least onesubstituent independently selected from the group consisting ofC₅₋₆-cycloalkyl, phenyl and 5 to 9 membered heteroaryl, substitutedC₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkenyl, at each occurrence,are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, which aresubstituted with at least one substituent independently selected fromthe group consisting of C₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, phenyl and 5 to 9membered heteroaryl, substituted C₆₋₁₀-aryl, substituted 5 to 12membered heteroaryl, substituted 6 membered aromatic ring system, andsubstituted 5 to 9 membered heteroaromatic ring system, at eachoccurrence, are C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, 6 memberedaromatic ring system, respectively, 5 to 9 membered heteroaromatic ringsystem, which are substituted with at least one substituentindependently selected from the group consisting of C₁₋₂₀-alkyl,C₅₋₆-cycloalkyl, phenyl, 5 to 9 membered heteroaryl, and at least oneCH₂-group, but not adjacent CH₂-groups, of C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkyl, can bereplaced by the linking group O. 6: The compound of claim 1, wherein: Xis S, R¹ is selected from the group consisting of C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl,C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl andsubstituted C₅₋₈-cycloalkenyl, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ areindependently from each other selected from the group consisting of H,C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₅₋₈-cycloalkyl, and substitutedC₅₋₈-cycloalkyl, substituted C₁₋₃₀-alkyl and substituted C₂₋₃₀-alkenyl,at each occurrence, are C₁₋₃₀-alkyl, respectively, C₂₋₃₀-alkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₅₋₆-cycloalkyl, phenyl and 5 to 9 memberedheteroaryl, and substituted C₅₋₈-cycloalkyl and substitutedC₅₋₈-cycloalkenyl, at each occurrence, are C₅₋₈-cycloalkyl,respectively, C₅₋₈-cycloalkenyl, which are substituted with at least onesubstituent independently selected from the group consisting ofC₁₋₂₀-alkyl, C₅₋₆-cycloalkyl, phenyl and 5 to 9 membered heteroaryl. 7:The compound of claim 1, wherein: X is S, R¹ is selected from the groupconsisting of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₂₋₃₀-alkenyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl and substituted C₅₋₈-cycloalkenyl, R², R⁴, R⁵, R⁶, R⁷and R⁹ are H, R³ and R⁸ are independently from each other selected fromthe group consisting of H, C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl,C₅₋₈-cycloalkyl and substituted C₅₋₈-cycloalkyl, substituted C₁₋₃₀-alkyland substituted C₂₋₃₀-alkenyl, at each occurrence, are C₁₋₃₀-alkyl,respectively, C₂₋₃₀-alkenyl, which are substituted with at least onesubstituent independently selected from the group consisting ofC₅₋₆-cycloalkyl and phenyl, and substituted C₅₋₈-cycloalkyl andsubstituted C₅₋₈-cycloalkenyl, at each occurrence, are C₅₋₈-cycloalkyl,respectively, C₅₋₈-cycloalkenyl, which are substituted with at least onesubstituent independently selected from the group consisting ofC₁₋₂₀-alkyl, C₅₋₆-cycloalkyl and phenyl. 8: A process for preparing thecompound of claim 1,

the process comprising treating a compound of formula (2):

with a compound of formula:R¹O—C(O)-LG, to obtain the compound of formula (1):

wherein: X is O, S or NR¹⁰; R¹⁰ is H C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₁₋₃₀-alkynyl or C(O)—OR¹¹; R¹ and R¹¹ are independentlyfrom each other selected from the group consisting of C₁₋₃₀-alkyl,substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl,C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substitutedC₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl, and substituted C₅₋₈-cycloalkenyl;R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ are independently from each otherselected from the group consisting of H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₂₋₃₀-alkynyl, C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl,C₅₋₈-cycloalkenyl, substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl,substituted O—C₁₋₃₀-alkyl, S—C₁₋₃₀-alkyl, substituted S—C₁₋₃₀-alkyl,C₆₋₁₄-aryl, substituted C₆₋₁₄-aryl, 5 to 15 membered heteroaryl,substituted 5 to 15 membered heteroaryl and halogen, or R² and R³, R³and R⁴, R⁴ and R⁵, R⁶ and R⁷, R⁷ and R⁸, or, R⁸ and R⁹ together with theC-atoms, to which they are connected, form a 6 to 10 membered aromaticring system, substituted 6 to 10 membered aromatic ring system, 5 to 12membered heteroaromatic ring system or a substituted 5 to 12 memberedheteroaromatic ring system; substituted C₁₋₃₀-alkyl, substitutedC₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkynyl, substituted O—C₁₋₃₀-alkyl andsubstituted S—C₁₋₃₀-alkyl, at each occurrence, are C₁₋₃₀-alkyl,C₁₋₃₀-alkenyl, C₂₋₃₀-alkynyl, O—C₁₋₃₀-alkyl, respectively,S—C₁₋₃₀-alkyl, which are substituted with at least one substituentindependently selected from the group consisting of C₅₋₆-cycloalkyl,C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a), OC(O)—R^(a),OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c), C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R, NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₅₋₈-cycloalkyl, and substituted C₅₋₈-cycloalkenyl, at eachoccurrence, are C₅₋₈-cycloalkyl, respectively, C₅₋₈-cycloalkenyl, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₁₋₂₀-alkenyl, C₂₋₂₀-alkynyl,C₅₋₆-cycloalkyl, C₆₋₁₀-aryl, 5 to 12 membered heteroaryl, OR^(a),OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b), C(O)—R^(a), C(O)—OR^(a),C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R, C(O)—NR^(a)—OR^(b),C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b), C(O)—SR^(a),NR^(a)R^(b), NR^(a)—NR^(b)R^(c), NR^(a)—C(O)R^(b), NR^(a)—C(O)—OR^(b),NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a), halogen, CN, and NO₂;substituted C₆₋₁₄-aryl, substituted 5 to 15 membered heteroaryl,substituted 6 to 10 membered aromatic ring system, and substituted 5 to12 membered heteroaromatic ring system, at each occurrence, areC₆₋₁₄-aryl, 5 to 15 membered heteroaryl, 6 to 10 membered aromatic ringsystem, respectively, 5 to 12 membered heteroaromatic ring system, whichare substituted with at least one substituent independently selectedfrom the group consisting of C₁₋₂₀-alkyl, C₂₋₂₀-alkenyl, C₂₋₂₀-alkynyl,C₅₋₆-cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, 5 to 12 memberedheteroaryl, OR^(a), OC(O)—R^(a), OC(O)—OR^(a), OC(O)—NR^(a)R^(b),C(O)—R^(a), C(O)—OR^(a), C(O)—NR^(a)R^(b), C(O)—NR^(a)—NR^(b)R^(c),C(O)—NR^(a)—OR^(b), C(O)—NR^(a)—C(O)—R^(b), C(O)—NR^(a)—C(O)—OR^(b),C(O)—SR^(a), NR^(a)R^(b) NR^(a)—NR^(b)R, NR^(a)—C(O)R^(b),NR^(a)—C(O)—OR^(b), NR^(a)—C(O)—NR^(b)R^(c), SR^(a), S—C(O)—R^(a),halogen, CN, and NO₂; at least one CH₂-group, but not adjacentCH₂-groups, of C₁₋₃₀-alkyl, substituted C₁₋₃₀-alkyl, C₂₋₃₀-alkenyl,substituted C₁₋₃₀-alkenyl, C₂₋₃₀-alkynyl, substituted C₂₋₃₀-alkynyl,C₅₋₈-cycloalkyl, substituted C₅₋₈-cycloalkyl, C₅₋₈-cycloalkenyl,substituted C₅₋₈-cycloalkenyl, O—C₁₋₃₀-alkyl, substituted O—C₁₋₃₀-alkyl,S—C₁₋₃₀-alkyl and substituted S—C₁₋₃₀-alkyl, can be replaced by alinking group selected from the group consisting of O, S, NR¹², CO,O—C(O), C(O)—O, O—C(O)—O, S—C(O), C(O)—S, NR¹²—C(O), C(O)—NR¹²,OC(O)—NR¹² and NR¹²—C(O)—O; R¹² is H, C₁₋₃₀-alkyl, substitutedC₁₋₃₀-alkyl, C₂₋₃₀-alkenyl, substituted C₂₋₃₀-alkenyl, C₂₋₃₀-alkynyl,substituted C₁₋₃₀-alkynyl or C(O)—OR^(d); R^(a), R^(b), Re and R^(d) areindependently from each other and at each occurrence selected from thegroup consisting of H, C₁₋₂₀-alkyl, C₁₋₂₀-alkenyl, C₂₋₂₀-alkynyl, C₅₋₆cycloalkyl, C₅₋₆-cycloalkenyl, C₆₋₁₀-aryl, and 5 to 12 memberedheteroaryl; and LG is a leaving group. 9: An electronic device,comprising the compound of claim
 1. 10: The electronic device of claim9, wherein the electronic device is an organic field effect transistor(OFET). 11: A semiconducting material, comprising the compound of claim1.